EP0058916B1 - Elektrisch leitfähige Polyolefinkunststoff-Zusammensetzung - Google Patents

Elektrisch leitfähige Polyolefinkunststoff-Zusammensetzung Download PDF

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Publication number
EP0058916B1
EP0058916B1 EP82101130A EP82101130A EP0058916B1 EP 0058916 B1 EP0058916 B1 EP 0058916B1 EP 82101130 A EP82101130 A EP 82101130A EP 82101130 A EP82101130 A EP 82101130A EP 0058916 B1 EP0058916 B1 EP 0058916B1
Authority
EP
European Patent Office
Prior art keywords
weight
parts
polyolefin resin
composition
ethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82101130A
Other languages
English (en)
French (fr)
Other versions
EP0058916A1 (de
Inventor
Yoichi Kawai
Yoshiro Nakamura
Yoshihisa Gotoh
Masami Maki
Sachio Yokote
Katsumi Sekiguchi
Katsuyoshi Sasagawa
Masao Imai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Toatsu Chemicals Inc
Original Assignee
Mitsui Toatsu Chemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP56023147A external-priority patent/JPS57137334A/ja
Priority claimed from JP2841381A external-priority patent/JPS57143339A/ja
Priority claimed from JP14797281A external-priority patent/JPS5852333A/ja
Priority claimed from JP17708081A external-priority patent/JPS5879041A/ja
Application filed by Mitsui Toatsu Chemicals Inc filed Critical Mitsui Toatsu Chemicals Inc
Publication of EP0058916A1 publication Critical patent/EP0058916A1/de
Application granted granted Critical
Publication of EP0058916B1 publication Critical patent/EP0058916B1/de
Expired legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur

Definitions

  • This invention relates to an electroconductive polyolefin resin composition which can be directly electroplated to provide a metal coating of excellent adhesion. More specifically, this invention relates to an electroconductive resin composition comprising (1) a polyolefin resin, (2) carbon black, (3) sulfur and (4) a specified plate adhesion promotor, i.e., trithiolcyanuric acid, which has excellent direct electroplatability and permits formation of a plated layer having uniform and good adhesion.
  • a specified plate adhesion promotor i.e., trithiolcyanuric acid
  • Polyolefin resins have previously been used also as base materials of plated articles, but since they are non electric conductors, they cannot be directly electroplated. Hence, electroplating of the polyolefin resin has been carried out after subjecting them to complex pre-treating steps such as degreasing by dipping in a warm alkaline solution, pre-etching by dipping in an organic solvent solution, etching by dipping in mixed chromic acid, sensitizing by dipping in an HCI-acidified solution of stannous chloride, activating by dipping in an HCI-acidified solution of palladium chloride, and electroless nickel plating by dipping in an alkaline or acidic nickel plating bath.
  • complex pre-treating steps such as degreasing by dipping in a warm alkaline solution, pre-etching by dipping in an organic solvent solution, etching by dipping in mixed chromic acid, sensitizing by dipping in an HCI-acidified solution of stannous chloride, activating by
  • Japanese Laid-Open Patent Publication JP-A-5460349 suggests a composition comprising a polyolefin resin, 25 to 41% of electrically conductive carbon black, 0.15 to 1.5% of sulfur, 0 to 7% of zinc oxide and 0.2 to 1.5% of mercaptobenzothiazole or mercaptobenzothiazyl disulfide.
  • This composition has the defects that the molding characteristics of the resin composition are poor and flow marks are seen to form on the surface of large-sized molded articles resulting in much impairment of the appearance of a plated layer formed thereon, and that much bleeding of compounding ingredients, particularly mercaptobenzothiazole, etc. occurs on the surface of the molded article.
  • an adhesion between the plated layer and the resin base can be obtained, it is not uniform or good.
  • JP-A-5558236 methods have been suggested which involve the addition of another type of vulcanization accelerator instead of the mercaptobenzothiazole or mercaptobenzothiazyl disulfide in the aforesaid composition, but they have similar defects.
  • an electroconductive polyolefin resin composition comprising (1) 100 parts by weight of a polyolefin resin, (2) 10 to 60 parts by weight of carbon black, (3) 0.1 to 6 parts by weight of sulfur and (4) at least 0.1 part by weight of trithiolcyanuric acid has good direct electroplatability; that no bleeding of the compounding ingredients on the surface of a molded article of the composition is observed; and that a plated layer on the molded article has uniform and good adhesion to any part of the surface of the molded article.
  • polystyrene resin used in this invention examples include polypropylene-type resins such as a propylene homopolymer, an ethylene/ propylene copolymer, an ethylene/propylene random copolymer rubber, and an ethylene/ propylene non-conjugated diene copolymer rubber, polyolefin resins selected from polyethylene and polyisobutylene, and blends of two or more or these polyolefin resins.
  • polypropylene-type resins such as a propylene homopolymer, an ethylene/ propylene copolymer, an ethylene/propylene random copolymer rubber, and an ethylene/ propylene non-conjugated diene copolymer rubber
  • polyolefin resins selected from polyethylene and polyisobutylene and blends of two or more or these polyolefin resins.
  • polyolefin resins having a melt flow index (determined by ASTM D-1238; to be abbreviated as MI hereinafter) of at least 20.
  • Carbon blacks sold generally on the market can be used in the present invention, and there is no particular restriction on the type of carbon black used. Examples are acetylene black obtained by the acetylene method, furnace black obtained by the furnace black method, thermal black by the natural gas thermal method, lump black, and conductive carbon black.
  • the conductive carbon black is especially preferred in view of its electric conductivity and flowability.
  • the amount of carbon black added is 10 to 60 parts by weight, preferably 10 to 40 parts by weight, per 100 parts by weight of the polyolefin resin. When the amount of the carbon black exceeds 60 parts by weight, the resulting composition gives too hard a molded article and the flowability of the composition during molding is inferior. When the amount of carbon black is less than 10 parts by weight, the composition has too high an electric resistance and its electroplatability is reduced.
  • Sulfur used in this invention may be in any form if it is elemental. Powdery sulfur is convenient to use.
  • the amount of sulfur added is 0.1 to 6 parts by weight, preferably 0.3 to 5 parts by weight, on the same basis. When the amount is less than 0.1 part by weight, the adhesion of the plated layer decreases. When the amount exceeds 6 parts by weight, the adhesion of the plated layer similarly decreases.
  • Trithiolcyanuric acid is a compound having a melting point of 280°C and is essential in the composition of this invention in order to obtain a uniform and good adhesion of plated coatings.
  • the amount of trithiolcyanuric acid is 0.1 to 5 parts by weight, preferably 0.3 to 2 parts by weight, more preferably 0.3 to 1.0 part by weight, on the same basis. If the amount is less than 0.1 part by weight, it is impossible to obtain an effect of increasing the adhesion of plated coatings, particularly the effect of reducing variations in the adhesion strength of a plated coating according to the sites of a molded article. If it exceeds 6 parts by weight, the effect of increasing and making the adhesion strength uniform cannot be expected.
  • the composition of this invention is performed by melt-extrusion using a single-screw extruder, a twin-screw extruder, etc. which are generally used in the art.
  • the composition is pelletized.
  • the extruding temperature is set as low as possible in order to avoid heat decomposition of the resin.
  • a phenolic antioxidant such as tetrakis - [methylene - 3 - (3',5' - di - t - butyl - 4' - hydroxyphenyl)propionate] methane and 2,6 - di - t - butyl - p - cresol as a stabilizer to oxygen and heat, a metal deterioration inhibitor such as malamine, a filler, a slip agent, a blowing agent and a fire retardant such as antimony trioxide and halogenated hydrocarbons which are generally used for polyolefin resins in the art.
  • a phenolic antioxidant such as tetrakis - [methylene - 3 - (3',5' - di - t - butyl - 4' - hydroxyphenyl)propionate] methane and 2,6 - di - t - butyl - p - cresol as a stabilizer to oxygen and heat,
  • atactic polypropylene may also be added to the polyolefin resin composition in order to increase its flowability during molding and to shorten the time during which a molded article after molding is left to stand before it is electroplated.
  • the electroconductive resin composition of this invention has an electric resistance of usually not more than 10 3 ohms although it may vary depending upon the types of the polyolefin resin, carbon black, etc. used. In view of operability in plating, the electrical resistance of the resin composition is preferably not more than 300 ohms.
  • the resin composition of this invention sc obtained can be molded into a desired molded article by various molding methods such as injection molding, extrusion molding and compression molding.
  • Plating of a molded article formed from the electroconductive resin composition of this invention is carried out, for example, by washing it with a weakly alkaline detergent and water, first electroplating the washed article from a Watts bath at a low voltage, for example for 3 minutes at 1 volt, and for 3 minutes at 1.5 volts, and then electroplating it under ordinary electroplating conditions.
  • a weakly alkaline detergent and water for example for 3 minutes at 1 volt, and for 3 minutes at 1.5 volts
  • electroplating it under ordinary electroplating conditions For example, it is possible to perform nickel strike plating to a thickness of 3 pm, copper plating to a thickness of 10 pm, then nickel plating to a thickness of 10 I lm, and chrome plating to a thickness of 0.1 Ilm in each layer.
  • the plated coatings so formed on the molded article of the composition of this invention have uniform and very good adhesion, and show sufficient durability against a heat cycle test.
  • the electric resistance of the resin is determined by measuring the resistance of a 1 cm- interval of the surface of a molded article by means of a tester.
  • the adhesion strength between the plated coating and the resin is determined by providing cuts with a width of 1 cm in the plated layer, peeling the plated layer from the resin layer in a direction at an angle of 180°, and measuring the peel strength at the time of peeling by means of a tensile tester at a stretching speed of 30 mm/min.
  • the heat cycle test is a method of evaluating the adhesion of a plated coating which comprises maintaining a plated test sample for 2 hours in a constant temperature chamber kept at 85°C, then allowing it to stand in the chamber until the temperature of the chamber is lowered to room temperature, then maintaining it for 2 hours at -30°C, allowing it to stand until the temperature rises to room temperature, and repeating this heating-cooling cycle 10 times, and thereafter observing the plated surface of the sample for the occurrence of cracks, blisters, etc.
  • the flat plate was electroplated for 5 minutes at 1 A/dm 2 in Watts bath at pH 4.2 containing 280 g/I of Ni(SO 4 ) 2 ⁇ 6H 2 O, 50 g/I of NiCl 2 ⁇ 6H 2 O and 45 g/I of boric acid to form a nickel plated coating. It was further electroplated in a copper plating bath containing 220 g/I of Cu(S0 4 ) z - 5H 2 0 and 55 g/I of H 2 SO 4 at 2.8 A/dm 2 for 90 minutes to obtain a copper-plated layer having a thickness of 50 pm.
  • Pellets were obtained and molded into a flat plate in the same way as in Example 1 except that the amount of trithiolcyanuric acid was changed to 1.0 part by weight.
  • the resulting flat plate had an electric resistance of 32 ohms.
  • the flat plate was subjected to nickel plating and copper plating under the same conditions as in Example 1, and the adhesion of the plated layer to the resin was measured in the same way as in Example 1, and found to be 2.5, 2.5, 2.6 and 2.6 kg/cm, respectively, showing uniform adhesion strength.
  • the resulting plated sample was subjected to the same heat cycle test as in Example 1, no change was noted on the plated surface of the sample.
  • Example 1 The procedure of Example 1 was followed except that 60 parts by weight of a propylene homopolymer (J4H, a trade name for a product of Mitsui Toatsu Chemicals, Inc.; MI 20 g/10 min.) and 40 parts by weight of an ethylene/propylene random copolymer (Toughmer P0280, a trade name for a product of Mitsui Petrochemical Industries, Ltd.) were used instead of the polyolefin resin used in Example 1.
  • the resulting fiat plate had an electric resistance of 36 ohms.
  • the adhesion strength of the plated layer was 2.0, 2.0, 2.0 and 2.1 kg/cm, respectively, from the gate portion. No change was noted in the plated surface of the sample by the cooling-heating cycle test.
  • Example 1 The procedure of Example 1 was followed except that 80 parts by weight of an ethylene/ propylene copolymer (BJ4H, a trade name for a product of Mitsui Toatsu Chemicals, Inc.: Mi 20 g/10 min.) and 20 parts by weight of an ethylene/ propylene random copolymer (Toughmer P0280, a trade name for a product of Mitsui Petrochemical Industries, Ltd.) were used instead of the polyolefin resin in Example 1.
  • BJ4H ethylene/ propylene copolymer
  • Mi 20 g/10 min. an ethylene/ propylene random copolymer
  • the resulting flat plate had an electric resistance of 35 ohms.
  • the adhesion strength of the plated layer was 2.1, 2.1, 2.2 and 2.1 kg/cm, respectively, from the gate portion. In the cooling-heating cycle test, no change was noted in the plate surface of the sample.
  • Pellets were produced and molded into a flat plate in the same way as in Example 1 except that trithiolcyanuric acid was not used.
  • the flat plate was subjected to nickel plating and copper plating under the same conditions as in Example 1, and the adhesion strength of the plated layer with respect to the resin article was measured by the same method as in Example 1. Furthermore, the electroplated sample was subjected to the same heat cycle test as in Example 1. The electric resistances of the flat plate was also measured. The results are shown in the following table.
  • Pellets were produced and molded into a flat plate in the same way as in Example 1 except that mercaptobenzothiazole was added instead of trithiolcyanuric acid.
  • the flat plate was subjected to nickel plating and copper plating under the same conditions as in Example 1, and the adhesion strength of the plated layer with respect to the resin article was measured by the same method as in Example 1.
  • the electroplated sample was also subjected to the same heat cycle test as in Example 1. The electric resistance of the flat plate was also measured. The results are shown in the following table.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Conductive Materials (AREA)

Claims (6)

1. Elektrisch leitfähige Polyolefinkunststoff-Zusammensetzung, die
(1) 100 Gewichtsteile eines polyolefinharzes,
(2) 10 bis 60 Gewichtsteile Ruß,
(3) 0,1 bis 6 Gewichtsteile Schwefel und
(4) wenigstens 0,1 Gewichtsteile Trithiocyanursäure umfaßt.
2. Zusammensetzung nach Anspruch 1, bei der die Menge der hinzugegebenen Trithiocyanursäure 0,3 bis 2 Gewichtsteile beträgt.
3. Zusammensetzung nach Anspruch 1, bei der das PofyoLfinharz ein Harz vom Polypropylen-Typ ist.
4. Zusammensetzung nach Anspruch 3, bei der das Harz vom Polypropylen-Typ ein Äthylen/Propylen-Copolymer, eine Kombination eines Propylenhomopolymeren mit einem Äthylen/Propylen-Copolymergummi mit Zufallsstruktur oder eine Kombination eines Äthylen/Propylen-Copolymeren mit einem Äthylen/Propylen-Copolymergummi mit Zufallsstruktur ist.
5. Zusammensetzung nach Anspruch 1, bei der das Mischen des Polyolefinharzes, des Rußes, des Schwefels und der Trithiocyanursäure durch ein Schmelz-Extrudieren durchgeführt wird.
6. Zusammensetzung nach Anspruch 1, die 100 Gewichtsteile des Polyolefinharzes, 10 bis 60 Gewichtsteile Ruß, 0,1 bis 6 Gewichtsteile Schwefel, 0,3 bis 2 Gewichtsteile Trithiocyanursäure und 5 bis 60 Gewichtsteile eines Fließverbesserungsmittels, das als Bestandteil (1) ungeeignet ist, nämlich ataktisches Polypropylen, umfaßt.
EP82101130A 1981-02-20 1982-02-16 Elektrisch leitfähige Polyolefinkunststoff-Zusammensetzung Expired EP0058916B1 (de)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP23147/81 1981-02-20
JP56023147A JPS57137334A (en) 1981-02-20 1981-02-20 Electrically-conductive resin composition
JP2841381A JPS57143339A (en) 1981-03-02 1981-03-02 Electrically conductive resin composition
JP28413/81 1981-03-02
JP147972/81 1981-09-21
JP14797281A JPS5852333A (ja) 1981-09-21 1981-09-21 導電性樹脂組成物
JP17708081A JPS5879041A (ja) 1981-11-06 1981-11-06 導電性樹脂組成物
JP177080/81 1981-11-06

Publications (2)

Publication Number Publication Date
EP0058916A1 EP0058916A1 (de) 1982-09-01
EP0058916B1 true EP0058916B1 (de) 1986-11-20

Family

ID=27457908

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82101130A Expired EP0058916B1 (de) 1981-02-20 1982-02-16 Elektrisch leitfähige Polyolefinkunststoff-Zusammensetzung

Country Status (4)

Country Link
EP (1) EP0058916B1 (de)
KR (1) KR860000786B1 (de)
CA (1) CA1180835A (de)
DE (1) DE3274400D1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2173200B (en) * 1985-03-30 1989-10-11 Charles Romaniec Conductive materials
US5629050A (en) * 1995-08-30 1997-05-13 The Dow Chemical Company Process for preparing coated articles

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5558236A (en) * 1978-10-24 1980-04-30 Showa Yuka Kk Olefin resin composition having improved electroplating property

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1769778A1 (de) * 1968-07-11 1971-12-30 Degussa Verfahren zur Vorbehandlung von Kunststoffen zum Zwecke der haftfesten Metallisierung
FR2079724A5 (de) * 1970-02-10 1971-11-12 Michelin & Cie

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5558236A (en) * 1978-10-24 1980-04-30 Showa Yuka Kk Olefin resin composition having improved electroplating property

Also Published As

Publication number Publication date
KR830009163A (ko) 1983-12-17
KR860000786B1 (ko) 1986-06-25
DE3274400D1 (en) 1987-01-08
CA1180835A (en) 1985-01-08
EP0058916A1 (de) 1982-09-01

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